• Nanocrystals;
  • Titanium di­oxide;
  • Boron;
  • Doping;
  • Crystal engineering


A simple synthesis was applied and tested for the preparation of boron-doped titanium dioxide [TiO2(B)] nanocrystals using titanium tetraisopropoxide (TTIP) together with boric acid (H3BO3) and benzyl alcohol as reaction solvent. Changes in the TTIP/H3BO3 molar ratio allowed a scalable synthetic protocol with a significant B-dopant control. In particular, this approach does not need surfactants or a final calcination step. X-ray diffractometry (XRD), low- and high-resolution transmission electron microscopy (TEM and HRTEM), and micro Raman spectroscopy revealed that the TiO2 nanocrystals produced have diameters up to about 10 nm and are mainly of the anatase phase but that a brookite phase was progressively formed with increased dopant level. The amount of boron was measured by inductively coupled plasma atomic emission spectroscopy (ICP-AES), and the presence of boron inside the crystals was determined by 11B cross-polarized magic-angle spinning nuclear magnetic resonance (11B CP-MAS NMR) spectroscopy. X-ray photoelectron spectroscopy (XPS) revealed the presence of boron on the nanocrystal surfaces, confirming the trend in the dopant concentration already observed with ICP-AES elemental analysis. Microphotoluminescence studies indicated the formation of three different typical luminescent defect states in correlation with the amount of added boron in the titania. UV/Vis absorption spectra showed a boron-dependent redshift of the absorption edge.